KR940000628B1 - Process for preparing polyoxyalkylene polyamine having terminal secondary amino group - Google Patents
Process for preparing polyoxyalkylene polyamine having terminal secondary amino group Download PDFInfo
- Publication number
- KR940000628B1 KR940000628B1 KR1019930017446A KR930017446A KR940000628B1 KR 940000628 B1 KR940000628 B1 KR 940000628B1 KR 1019930017446 A KR1019930017446 A KR 1019930017446A KR 930017446 A KR930017446 A KR 930017446A KR 940000628 B1 KR940000628 B1 KR 940000628B1
- Authority
- KR
- South Korea
- Prior art keywords
- alcohol
- amino group
- secondary amino
- polyoxyalkylene
- polyoxyalkylene polyamine
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
내용 없음.No content.
Description
본 발명은, 분자말단에 2급아미노기를 가진 폴리옥시알킬렌폴리아민의 제조방법에 관한 것으로, 더 상세하게는, 수소화-탈수소촉매의 존재하에 폴리옥시알킬렌폴리올과 1급아민화합물을 반응시켜서, 분자말단에 2급아미노기를 가진 폴리옥시알킬렌폴리아민을 제조하는 방법에 있어서, 이 반응을 1가알코올의 공존하에 실시하는 것을 특징으로 하는 제조방법에 관한 것이다. 말단에 아미노기를 가진 폴리에테르는 폴리이소시아네이트와의 중부가반응기에 의해 폴리우레아를 제공하고, 폴리우레아계의 RIM, 엘라스토머, 연질포옴, 경질포옴등의 원료로서 사용된다. 또, 에폭시수지, 폴리아미드, 폴리이미등의 각종 플라스틱원료로서 유용한 화합물이다.The present invention relates to a method for producing a polyoxyalkylene polyamine having a secondary amino group at the molecular end, and more particularly, by reacting a polyoxyalkylene polyol and a primary amine compound in the presence of a hydrogenation-dehydrogenation catalyst, A method for producing a polyoxyalkylene polyamine having a secondary amino group at its molecular end, wherein the reaction is carried out in the presence of a monohydric alcohol. A polyether having an amino group at its end provides a polyurea by means of a polyaddition reactor with polyisocyanate, and is used as a raw material of polyurea-based RIM, elastomer, soft foam, hard foam and the like. Moreover, it is a compound useful as various plastic raw materials, such as an epoxy resin, a polyamide, and a polyimide.
폴리옥시알킬렌폴리올과 암모니아 또는 아민화합물을 반응시켜서, 말단에 아미노기를 가진 폴리옥시알킬렌폴리아민을 얻는 방법은 공지이다. 예를들면, 벨기에 특허 677124호에서, 폴리옥시알킬렌폴리올과 암모니아를, 라니(Raney) 금속촉매를 사용해서 고온고압하에 반응시켜서 제조하는 방법에 제안되어 있다. 이 방법에 의하면, 생성하는 폴리옥시알킬렌폴리올의 말단아미노기는 모두 1급아민이 된다. 말단이 1급아미노기의 폴리옥시알킬렌폴리아민은, 이소시아네이트와의 반응성이 높기 때문에, 우레아화반응을 제어하기 어렵고, 특수하고, 고가인 고속용 성형기가 필요하게 되는 등의 문제점을 가진다. 한편, 1급아미노기에 비해서 2급아미노기를 가진 폴리옥시알킬렌폴리아민은, 이소시아네이트와의 반응성이 완만하기 때문에, 우레아화반응을 제어하기 쉽고, 성형이 용이하다고 하는 큰장점이 가진다. 2급아미노기를 가진 폴리옥시알킬렌폴리아민의 제조방법으로서는, 일본국 특공소 45-7289호 공보에, 폴리옥시알킬렌폴리올과 암모니아 또는 1급아민을, 라니금속촉매를 사용해서 고온고압하에 반응시켜서 제조하는 방법이 제안되고 있다. 그러나, 오직 암모니아와 반응해서 얻게되는 2급아미노기를 가진 폴리옥시알킬렌폴리아민은, 분자간반응에 의하지 않으면 생성되지 않고, 분자말단에 아미노기를 지닌 것은 아니다. 또, 1급아민화합물과 반응시켜서 제조된 것도, 마찬가지로 분자간 축합한 폴리옥시알킬렌폴리아민을 가능성이 높다. 그래서, 본 발명자들이 이것에 기초하여 실험하였던 바, 뒤에 설명하는 비교예 4에 표시되는 바와같이, 생성물속에 명백히 2급아민에서 유래하는 질소는 검출되었으나, 전체아민가 및 미반응의 수산기가의 합계가, 원료폴리옥시알킬렌폴리올의 수산기가보다도 크게 저하해 있고, 분자간 축합한 폴리옥시알킬렌폴리아민인 것이 인정되었다. 따라서, 이 방법으로 얻게되는 2급아민은, 본 발명의 분자말단에 2급아미노기를 가진 폴리옥시알킬렌폴리아민과는 구조를 달리한다.The method of making polyoxyalkylene polyamine which has an amino group at the terminal by making polyoxyalkylene polyol react with ammonia or an amine compound is known. For example, Belgian Patent 677124 proposes a method for producing polyoxyalkylene polyols and ammonia by reacting them under high temperature and high pressure using a Raney metal catalyst. According to this method, the terminal amino groups of the polyoxyalkylene polyol to be produced are all primary amines. Since the polyoxyalkylene polyamine of the terminal amino group has high reactivity with isocyanate, it is difficult to control the ureaization reaction and has a problem such as a special, expensive high speed molding machine is required. On the other hand, polyoxyalkylene polyamines having a secondary amino group as compared to the primary amino group have a large advantage of being easy to control the urea reaction and easy to mold because of its moderate reactivity with isocyanates. As a method for producing a polyoxyalkylene polyamine having a secondary amino group, Japanese Unexamined Patent Publication No. 45-7289 reacts polyoxyalkylene polyol with ammonia or primary amine under high temperature and high pressure using a Raney metal catalyst. The manufacturing method is proposed. However, a polyoxyalkylene polyamine having a secondary amino group obtained only by reaction with ammonia is not produced unless it is an intermolecular reaction, and does not have an amino group at the end of the molecule. Moreover, the thing manufactured by making it react with a primary amine compound also has high possibility the polyoxyalkylene polyamine condensed intermolecularly. Thus, the inventors experimented based on this, and as shown in Comparative Example 4 described later, nitrogen apparently derived from the secondary amine was detected in the product, but the sum of the total amine value and the unreacted hydroxyl value was It was recognized that the hydroxyl value of the raw material polyoxyalkylene polyol was significantly lower than that of the polyoxyalkylene polyamine condensed intermolecularly. Therefore, the secondary amine obtained by this method has a structure different from the polyoxyalkylene polyamine which has a secondary amino group in the molecular terminal of this invention.
본 발명의 목적은, 폴리옥시알킬렌폴리올과 1급아민화합물을 반응시켜, 분자말단에 2급아미노기를 가진 폴리옥시알킬렌폴리아민을 제고하는 방법에 있어서,분자간반응을 억제하고, 분자말단의 2급아민의 함량이 높은 폴리옥시알킬렌폴리아민을 얻는 방법을 제공하는데 있다.An object of the present invention is to react a polyoxyalkylene polyol with a primary amine compound to produce a polyoxyalkylene polyamine having a secondary amino group at the molecular end thereof. It is to provide a method for obtaining a polyoxyalkylene polyamine having a high content of a tertiary amine.
본 발명자들은, 상기 목적을 달성하기 위해 예의 검토한 결과, 수소화-탈수소화촉매의 존재하에 폴리옥시알킬렌폴리올과, 1급아민화합물을 반응시켜서 분자말단에 2급아미노기를 지닌 폴리옥시알킬렌폴리아민을 제조하는 방법에 있어서, 이 반응을 1가알코올의 공존하에 실시하면 2급아민 선택율이 향상된다는 것을 발견하여 본 발명을 완성하게 되었다.MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors made the polyoxyalkylene polyamine which has a secondary amino group at the molecular end by making polyoxyalkylene polyol react with a primary amine compound in presence of a hydrogenation-dehydrogenation catalyst. In the process for preparing the reaction, the present invention was found to be improved in the secondary amine selectivity when the reaction was carried out in the presence of monohydric alcohol.
즉, 본 발명은 수소화-탈수소촉매의 존재하에, 폴리옥시알킬렌폴리올과 1급아민화합물을 반응시켜서 분자말단에 2급아미노기를 가진 폴리옥시알킬렌폴리아민을 제조하는 방법에 있어서, 이 반응을 1가알코올의 공존하에 실시하는 것을 특징으로 하는 방법이다.That is, the present invention is a method for producing a polyoxyalkylene polyamine having a secondary amino group at the molecular end by reacting a polyoxyalkylene polyol and a primary amine compound in the presence of a hydrogenation-dehydrogenation catalyst. It is a method characterized by carrying out in coexistence of an alcohol.
본 발명에서 사용하는 폴리옥시알킬렌폴리올이란, 2~8관능성으로, 평균분자량 400~30000의 것이 적당하다. 예를들면, 에틸렌글리콜, 디에틸렌글리콜, 프로필렌글리콜, 디프로필렌글리콜, 1,4-부틸렌글리콜 등의 디올류, 글리세린, 헥산트리올, 트리메틸롤프로판, 펜타에리트리톨, 소르비톨, 스크로오스등의 폴리올류, 비스페놀 A, 비스페놀 F, 디히드록시페닐에테르, 디히드록시비페닐, 히드로퀴논, 레조르신, 클로로글루신, 나프탈렌디올, 아미노페놀, 아미노나프톨, 페놀포름알데히드 축합물등의 방향족화합물, 메틸디에탄올아신, 에틸디이소프로판올아민, 트리에탄올아민, 에틸린디아민, 헥사메틸렌디아민, 비스(p-아미노시클로헥실)메탄, 톨린렌디아민, 디페닐메탄디아민, 나프탈렌디아민등의 아민화합물등, 또는 상기 화합물중에서 선택된 2종이상의 혼합물에, 에틸렌옥시드, 프로필렌옥시드, 부틸렌옥시드, 스티렌옥시드 등을 1종 또는 2종이상 부가시켜서 얻게되는 폴리옥시알킬렌폴리올이다. 상기한 것외에, 테트라히드로푸란의 개환중합에 의해서 얻게되는 폴리테트라메틸렌에테르글리콜등도 예로들 수 있다. 또 상기 폴리옥시알킬렌폴리올중에서 선택된 2종이상의 혼합물도 사용할 수 있다.The polyoxyalkylene polyol used by this invention is 2-8 functional, and the thing of average molecular weights 400-30000 is suitable. For example, diols, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1, 4- butylene glycol, glycerin, hexane triol, trimethylol propane, pentaerythritol, sorbitol, cellulose, etc. Aromatic compounds, such as polyols, bisphenol A, bisphenol F, dihydroxy phenyl ether, dihydroxy biphenyl, hydroquinone, resorcin, chloroglucin, naphthalenediol, aminophenol, amino naphthol, phenol formaldehyde condensate, methyl Amine compounds such as diethanol acin, ethyldiisopropanolamine, triethanolamine, ethylindiamine, hexamethylenediamine, bis (p-aminocyclohexyl) methane, tolinenediamine, diphenylmethanediamine, naphthalenediamine, and the like Ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like are added to two or more kinds of mixtures selected from Polyoxyalkylenepolyols obtained. In addition to the above-mentioned, polytetramethylene ether glycol etc. which are obtained by ring-opening polymerization of tetrahydrofuran are mentioned. Moreover, the mixture of 2 or more types chosen from the said polyoxyalkylene polyol can also be used.
본 발명에서 사용하는 1급아민화합물로서는, 통상 탄소수 1~20정도의 아민이고, 구체적으로 메틸아민, 에틸아민, n-프로필아민, 이소프로필아민, 부틸아민, 이소부틸아민, sec-부틸아민, t-부틸아민, 아밀아민, 헥실아민, 헵틸아민, 옥틸아민, 노닐아민, 데실아민, 도데실아민(라우릴아민), 테트라데실아민(미리스틸아민), 헥사데실아민(팔미틸아민), 옥타데실아민(스테아릴아민), 올레일아민등의 알킬아민, β-아미노프로필메틸에테르, β-아미노프로필에틸에테르등의 치환기를 가진 알킬아민, 벤질아민, p-메틸벤질아민등의 아랄킬아민, 시클로펜틸아민, 시클로헥실아민등의 지환족아민을 예로들 수 있다. 또 상기 1급아민중에서 선택된 2종이상의 혼합물로 사용된다.As a primary amine compound used by this invention, it is a C1-C20 amine normally, specifically, methylamine, ethylamine, n-propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, t-butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine (laurylamine), tetradecylamine (myristolamine), hexadecylamine (palmitylamine), Aralkyl, such as alkylamine, such as octadecylamine (stearylamine) and oleylamine, alkylamine which has substituents, such as (beta) -aminopropylmethyl ether and (beta) -aminopropylethyl ether, benzylamine, and p-methylbenzylamine Alicyclic amines, such as an amine, a cyclopentylamine, and a cyclohexylamine, are mentioned. It is also used as a mixture of two or more selected from the above-mentioned primary amines.
본 발명의 방법에서 사용하는 수소화-탄소수 촉매로서는, 종래 공지의 촉매를 사용할 수 있고, 예를들면 Ni,Co 등을 규조토, 알루미나와 같은 담체에 담지시킨 담지형 촉매, Ni,Co계의 라니형 촉매, Cu-Cr계 촉매등이 대표적인 예이다. 그중에서도 담지형 촉매는 특히 호적한 촉매의 하나이다.As the hydrogenation-carbon number catalyst used in the method of the present invention, a conventionally known catalyst can be used. For example, a supported catalyst having Ni, Co and the like supported on a carrier such as diatomaceous earth and alumina, or a Ni, Co-based Raney type Catalysts, Cu-Cr-based catalysts and the like are representative examples. Among them, the supported catalyst is one of particularly suitable catalysts.
본 발명에 있어서, 1가알코올을 공존시키므로서 2급아민선택율의 대표적인 향상이 이루어지는데, 공존시키는 1가알코올로서는, 탄소수 1~20, 바람직하게는 1~10의 1급 또는 2급 알코올류를 들 수 있다. 구체적으로는, 메탄올, 에탄올, n-프로판올, 이소프필일코올, n-부틸알코올, 이소부틸알코올, sec-부틸알코올, 아밀알코올, 헥실알코올, 헵틸알코올, 옥틸알코올, 노닐알코올, 데실알코올 등의 알킬알코올류, β-히드로프로필메틸에테르, β-히드로프로필에틸에테르 등의 치환기를 가진 알킬알코올류, 벤질알코올, p-메틸벤질알코올, p-메틸벤질알코올 등의 아랄킬알코올류, 시클로펜틸알코올, 시클로헥실알코올등의 시클로알킬알코올을 예로 들 수 있다. 통상, 본 발명에 사용하는 1가알코올은, 특히 제한을 받는 것은 아니지만, 1급아민화합물과 동일한 탄소수를 가지고, 또한 동일한 탄소결합양식의 것이 특히 바람직하다.In the present invention, a typical improvement of the secondary amine selectivity is achieved by coexisting monohydric alcohols. As monohydric alcohols to coexist, primary or secondary alcohols having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms are used. Can be mentioned. Specifically, alkyl such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, etc. Alkyl alcohols having substituents such as alcohols, β-hydropropylmethyl ether and β-hydropropylethyl ether, aralkyl alcohols such as benzyl alcohol, p-methylbenzyl alcohol and p-methylbenzyl alcohol, cyclopentyl alcohol, Cycloalkyl alcohols, such as cyclohexyl alcohol, are mentioned. Usually, although the monohydric alcohol used for this invention is not restrict | limited especially, the thing of the same carbon bond type as the primary amine compound, and of the same carbon bonding mode is especially preferable.
본 발명에서 사용되는 1급아민화합물의 양은, 용도에 따라 결정되지만, 통상, 수산기에 대해서 0.5~50당량, 바람직하게는 0.8~10당량, 가장 바람직하게는 1~5당량이 사용된다.Although the quantity of the primary amine compound used by this invention is determined according to a use, 0.5-50 equivalent, Preferably it is 0.8-10 equivalent, Most preferably 1-5 equivalent is used with respect to a hydroxyl group.
본 발명에 사용되는 1가알코올의 양은, 통상, 아민화합물에 대해서 0.01~1당량, 바람직하게는 0.05~0.7당량, 가장 바람직하게는 0.1~0.5당량이 사용된다. 1가알코올의 양이 너무 작으면, 첨가효과가 없고, 너무 많으면, 폴리옥시알킬렌폴리올의 전화율이 너무 저하해서, 바람직하지 않다.The amount of monohydric alcohol used in the present invention is usually 0.01 to 1 equivalent, preferably 0.05 to 0.7 equivalent, and most preferably 0.1 to 0.5 equivalent with respect to the amine compound. If the amount of monohydric alcohol is too small, there is no addition effect. If the amount of monohydric alcohol is too large, the conversion ratio of the polyoxyalkylene polyol is too low, which is not preferable.
본 발명의 반응조건은, 특히 한정되는 것은 아니지만, 일반적으로는, 반응온도 150~280℃, 바람직하게는 180~250℃, 반응압력 20~150㎏/㎠G, 바람직하게는 30~100㎏/㎠G, 반응시간 1~20시간, 바람직하게는 5~10시간에서 행한다. 반응계내에, 수소를 공존시켜도 좋고, 안시켜서 좋다. 반응온도가 낮을수록, 반응속도가 작고, 또 너무 높으면 폴리옥시알킬렌폴리올이 분해해버리기 때문에 바람직하지 않다.Although the reaction conditions of this invention are not specifically limited, Generally, reaction temperature 150-280 degreeC, Preferably 180-250 degreeC, Reaction pressure 20-150 kg / cm <2> G, Preferably 30-100 kg / It is performed in cm 2 G, reaction time 1 to 20 hours, preferably 5 to 10 hours. In the reaction system, hydrogen may coexist or may not be present. The lower the reaction temperature, the lower the reaction rate, and the higher the reaction temperature, which is not preferable because the polyoxyalkylene polyol decomposes.
반응종료후는, 미반응아민화합물의 증발에 의한 회수, 촉매여별, 수세, 건조등의 방법을 적당히 조합하므로서, 목적물인, 분자말단에 2급아미노기를 가진 폴리옥시알킬렌폴리아민을 얻을 수 있다.After the completion of the reaction, a polyoxyalkylene polyamine having a secondary amino group at the end of the molecule can be obtained by appropriately combining methods such as recovery by evaporation of the unreacted amine compound, catalyst filtering, washing with water and drying.
다음, 실시예에 의해 본 발명을 설명한다.Next, an Example demonstrates this invention.
한편, 본원 발명에 사용된 종래의 촉매는 다음과 같이 제조한다.On the other hand, the conventional catalyst used in the present invention is prepared as follows.
[촉매조제예][Chemical preparation]
질산니켈[Ni(NO3)2·6H2O]1200g을 2600㎖의 증류수에 용해하고 규조토 370g을 첨가하여 80℃로 가열한다(용액 A), 한편, 890g의 탄산암모늄을 2300㎖의 증류수에 용해하고 85℃로 가열한다(용액 B). 용액 A를 잘 교반하면서, 이것에, 용액 B를 1시간에 걸쳐서 적하하고, 또 1시간 숙성한다. 흡인여과를 행하여 침전물을 분리하고, 온수에 의해 세정을 반복해서 알칼리를 제거하고, 110~120℃에서 15시간 건조한다. 건조된 케이크를 막자사발에서 분쇄하고, 석영관속에 사입하고, 관형상전기로를 사용해서, 300℃에서 3시간 소성한 후, 수소가스를 도입해서 1시간 환원해서 Ni-규조토촉매 640g을 얻는다.1200 g of nickel nitrate [Ni (NO 3 ) 2 .6H 2 O] is dissolved in 2600 ml of distilled water and heated to 80 ° C by adding 370 g of diatomaceous earth (solution A). Meanwhile, 890 g of ammonium carbonate is added to 2300 ml of distilled water. Dissolve and heat to 85 ° C. (Solution B). While stirring solution A well, solution B is dripped over 1 hour over this, and aged for 1 hour. The precipitate was separated by suction filtration, washed with hot water repeatedly to remove alkali, and dried at 110 to 120 ° C. for 15 hours. The dried cake is pulverized in a mortar, poured into a quartz tube, calcined at 300 ° C. for 3 hours using a tubular electric furnace, and then introduced with hydrogen gas to reduce for 1 hour to obtain 640 g of Ni-diatomaceous earth catalyst.
[실시예 1]Example 1
200㎖의 고압오오토클레이브에, 촉매조제예로 얻은 Ni규조토촉매(Ni함유율 50중량%) 4g, 글리세린에 프로필렌옥시드를 부가중합시켜서 얻게 되는 폴리옥시프로필렌트리올(수산기가 33.4mgKOH/g, 평균분자량 5040 ; 이하 폴리올 P라 한다) 80g, 이소프로필아민 14.2g, 이소프로필알코올 7.2g을, 이 순서로 사입하고, 질소치환을 5회(10kg/㎠G) 행한 후, 수소를 초기압력 50kg/㎠G로 사입한다. 교반하면서 220℃까지 승온하고, 8시간 반응을 행하였다. 이때 압력은 80kg ·㎠G이다. 반응종료후, 촉매여벌, 감압건조에 의해 분자말단에 2급아미노기를 가진 폴리옥시알킬렌폴리아민을 정제한다. 여기서 분자간결합율이란, 분자간 2급아민가의, 2급아민가에 대한 비율(%)이고, 분자간 2급아민가는, 하기의 식에서 산출한다.Polyoxypropylene triol obtained by addition polymerization of propylene oxide to 4 g of Ni-diatomaceous earth catalyst (Ni content 50 wt%) obtained in the preparation example of a catalyst in 200 ml of a high-pressure autoclave (hydroxyl value of 33.4 mgKOH / g, 80 g of average molecular weight (hereinafter referred to as polyol P)), 14.2 g of isopropylamine, and 7.2 g of isopropyl alcohol were introduced in this order, and nitrogen replacement was performed five times (10 kg / cm 2 G), and then hydrogen was initially loaded at 50 kg. It is injected at / cm 2 G. It heated up to 220 degreeC, stirring, and reaction was performed for 8 hours. At this time, the pressure is 80kgcm2G. After the completion of the reaction, the polyoxyalkylene polyamine having a secondary amino group at the terminal of the molecule is purified by catalytic separation and reduced pressure drying. Here, the intermolecular bond ratio is the ratio (%) of the intermolecular secondary amine value to the secondary amine value, and the intermolecular secondary amine value is calculated by the following formula.
이론아민가-(전체아민가+잔존수산기가)Theoretical amine value-(total amine value + remaining hydroxyl value)
결과를 제1표에 표시한다.The results are shown in the first table.
[실시예 2]Example 2
실시예 1에 있어서, 폴리올 P/이소프로필아민/이소프로필알코올의 당량비를 1/10/5로 바꾼 이외는 실시예 1과 동일조건에서 반응을 행한다. 이때의 압력은 85kg/㎠G 이다. 결과를 제1표에 표시한다.In Example 1, reaction is performed on the same conditions as Example 1 except having changed the equivalence ratio of polyol P / isopropylamine / isopropyl alcohol into 1/10/5. The pressure at this time is 85kg / cm 2 G. The results are shown in the first table.
[실시예 3]Example 3
실시예 1에 있어서, 폴리올 P/이소프로필아민/이소프로필알코올의 당량비를 1/20/5로 바꾼 이외는, 실시예 1과 동일조건에서 반응을 행한다. 이때의 압력은 92kg/㎠G 이다. 결과를 제1표에 표시한다.In Example 1, reaction is performed on the same conditions as Example 1 except having changed the equivalence ratio of polyol P / isopropylamine / isopropyl alcohol into 1/20/5. The pressure at this time is 92 kg / cm 2 G. The results are shown in the first table.
[실시예 4]Example 4
실시예 1에 있어서, 폴리올 P 대신, 글리세린에 프로필렌옥시드, 이어서 에틸렌옥시드를 부가중합시켜서 얻게되는 폴리옥시프로필렌 폴리옥시에틸렌트리올(에틸렌옥시드 함량 15wt%, 수산기가 33.30mgKOH/g, 평균분자량 5100 ; 이하 폴리올 Q라 한다)을 사용한 이외는, 실시예 1과 동일조건에서 반응을 행한다. 이때의 압력은 실시예 1과 동일하다. 결과를 제1표에 표시한다.In Example 1, polyoxypropylene polyoxyethylene triol obtained by addition polymerization of propylene oxide, followed by ethylene oxide, to glycerine instead of polyol P (ethylene oxide content of 15wt%, hydroxyl value of 33.30mgKOH / g, average The reaction is carried out under the same conditions as in Example 1 except that the molecular weight 5100 (hereinafter referred to as polyol Q) is used. The pressure at this time is the same as in Example 1. The results are shown in the first table.
[실시예 5]Example 5
실시예 1에 있어서, 폴리올 Q 대신에, 테트라히드로푸란의 개환중합에 의해서 얻게 되는 폴리테트라메틸렌에테르글리콜(수산기가 112mgKOH/g, 평균분자량 1000 ; 이하 폴리올 R이라 한다)을 사용한 이외는, 실시예 1과 동일조건에서 반응을 행한다. 이때의 압력은 실시예1과 동일하다. 결과를 제1표에 표시한다.Example 1 except that polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran instead of polyol Q (hydroxyl group 112 mgKOH / g, average molecular weight 1000; hereinafter referred to as polyol R) The reaction is carried out under the same conditions as 1. The pressure at this time is the same as in Example 1. The results are shown in the first table.
[실시예 6]Example 6
실시예 1에 있어서, 이소프로필아민, 이소프로필알코올대신, n-부틸아민, n-부틸알코올을 사용, 반응시간을 10시간으로 바꾼 이외는, 실시예 1과 동일조건에서 반응을 행한다. 이때의 압력은 78kg/㎠G이다. 결과를 제1표에 표시한다.In Example 1, reaction is performed on the same conditions as Example 1 except having changed the reaction time into 10 hours using n-butylamine and n-butyl alcohol instead of isopropylamine, isopropyl alcohol. The pressure at this time is 78 kg / cm 2 G. The results are shown in the first table.
[실시예 7]Example 7
실시예 1에 있어서, 이소프로필아민, 이소프로필알코올대신, 에틸아민, 에틸알코올을 사용한 이외는, 실시예 1과 동일조건에서 반응을 행한다. 이때의 압력은 82kg/㎠G이었다. 결과를 제1표에 표시한다.In Example 1, reaction is performed on the same conditions as Example 1 except having used isopropylamine, isopropyl alcohol, ethylamine, and ethyl alcohol. The pressure at this time was 82 kg / cm 2 G. The results are shown in the first table.
[실시예 8]Example 8
실시예 1에 있어서, 이소프로필알코올대신, 옥탄올을 사용한 이외는, 실시예 1과 동일조건에서 반응을 행한다. 이때의 압력은 73kg/㎠G이었다. 결과를 제1표에 표시한다.In Example 1, reaction is performed on the same conditions as Example 1 except having used octanol instead of isopropyl alcohol. The pressure at this time was 73 kg / cm 2 G. The results are shown in the first table.
[비교예 1]Comparative Example 1
실시예 1에 있어서, 이소프로필알코올을 공존시키지 않고 실시예 1과 동일조건에서 반응을 행한다. 이때의 압력은 73kg/㎠G이다. 결과를 제1표에 표시한다.In Example 1, the reaction is carried out under the same conditions as in Example 1 without isopropyl alcohol coexisting. The pressure at this time is 73 kg / cm 2 G. The results are shown in the first table.
[비교예 2]Comparative Example 2
실시예 2에 있어서, 이소프로필알코올을 공존시키지 않고, 실시예 2과 동일조건에서 반응 행한다. 이때의 압력은 88kg/㎠G이다. 결과를 제1표에 표시한다.In Example 2, reaction is performed under the same conditions as in Example 2 without isopropyl alcohol coexisting. The pressure at this time is 88 kg / cm 2 G. The results are shown in the first table.
[표 1]TABLE 1
수소화-탈수소촉매의 존재하에, 폴리옥시알킬렌폴리올과 1급아민화합물을 반응시켜서, 분자말단에 2급아미노기를 가진 폴리옥시알킬렌폴리아민을 제조하는 방법에 있어서, 이 반응을 1가알코올의 공존하에 실시하므로서, 종래보다도 2급아미노기 함량이 높은 폴리옥시알킬렌폴리아민을 얻는 것이 가능해진다.In a method of producing a polyoxyalkylene polyamine having a secondary amino group at the molecular end by reacting a polyoxyalkylene polyol with a primary amine compound in the presence of a hydrogenation-dehydrogenation catalyst, the reaction is coexisted with a monohydric alcohol. By carrying out under the present invention, it becomes possible to obtain a polyoxyalkylene polyamine having a higher content of secondary amino groups than before.
본 발명의 방법에 의해서 얻게되는 화합물은, 이소시아네이트와 반응해서 우레아결합에 의한 폴리우레아 수지를 얻는등의, 플라스틱원재료로서 유효하게 이용할 수 있다.The compound obtained by the method of the present invention can be effectively used as a plastic raw material, such as obtaining a polyurea resin by reacting with an isocyanate and obtaining a urea bond.
Claims (21)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32192788 | 1988-12-22 | ||
| JP63-321927 | 1988-12-22 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019890016619A Division KR940000627B1 (en) | 1988-11-16 | 1989-11-16 | Process for preparing polyoxyalkylene polyamine having terminal secondary amino group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR940000628B1 true KR940000628B1 (en) | 1994-01-26 |
Family
ID=18137970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019930017446A KR940000628B1 (en) | 1988-12-22 | 1993-09-02 | Process for preparing polyoxyalkylene polyamine having terminal secondary amino group |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR940000628B1 (en) |
-
1993
- 1993-09-02 KR KR1019930017446A patent/KR940000628B1/en not_active IP Right Cessation
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR940000627B1 (en) | Process for preparing polyoxyalkylene polyamine having terminal secondary amino group | |
| US4960942A (en) | Process for the manufacture of N-(polyoxyalkyl)-N-(alkyl)amines | |
| EP0045544B1 (en) | Process for the manufacture of polyether polyols and their use for preparing polyurethanes | |
| US3660319A (en) | Tertiary polyoxyalkylenepolyamines | |
| US4588840A (en) | Oxyalkylene aromatic amines | |
| EP0132290B1 (en) | Procedure for the partial alkoxylation of polyoxyalkylenamines | |
| US3161682A (en) | Method for preparing polyoxyalkylene primary amines | |
| US4927912A (en) | Secondary isopropyl amines derived from oxyalkylene triamines | |
| US5300559A (en) | Polyamines derived from THPB and processes for preparing the same | |
| US3832402A (en) | Tertiary polyoxyalkylenepolyamines | |
| KR940000628B1 (en) | Process for preparing polyoxyalkylene polyamine having terminal secondary amino group | |
| US5288873A (en) | Aminated alkoxylated imidazolidones | |
| KR940000629B1 (en) | Process for preparing polyoxyalkylene polyamine having terminal secondary amino group | |
| CA1207341A (en) | Diamines and a process for their preparation | |
| US6599952B2 (en) | Polyether polyols with increased functionality | |
| US3064001A (en) | Method for preparing piperazines | |
| CN116003775B (en) | Triamine polyether compound, and preparation method and application thereof | |
| EP0054430B1 (en) | Tertiary amino polyols | |
| US5424387A (en) | Di-amino compounds and processes for preparing the same | |
| US5354907A (en) | Amines derived from THPE and processes for preparing the same | |
| US4827038A (en) | Bis(diaminopolyalkoxy)-N-alkylamines by amination of hydroxyl-containing tertiary amines | |
| EP0180455A2 (en) | Process for the preparation of alkoxylated tertiary amine compounds | |
| CN105967983B (en) | The production method of low molecular polyether polyalcohol | |
| US5312990A (en) | Di-amino compounds | |
| JP2955328B2 (en) | Polyoxyalkylene polyol derivative and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A107 | Divisional application of patent | ||
| A201 | Request for examination | ||
| G160 | Decision to publish patent application | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20040120 Year of fee payment: 11 |
|
| LAPS | Lapse due to unpaid annual fee |